Insecticidal 1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadien-3-one (1,4,5,6-tetrahydro-2-pyrimidinyl)hydrazones

ABSTRACT

The invention is 1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadien-3-one (1,4,5,6-tetrahydro-2-pyrimidinyl)hydrazones which are useful insecticides.

This is a division of application Ser. No. 883,775 filed Mar. 6, 1978which is now U.S. Pat. No. 4,163,102 filed July 31, 1979 which was acontinuation-in-part application Ser. No. 793,116 filed May 2, 1977 nowabandoned.

The invention is compounds of the formula: ##STR1## wherein X ishydrogen or methyl which are useful as insecticides, especially for thecontrol of fire ants and cockroaches.

Pentadien-3-one substituted amido hydrazones are described in U.S. Pat.No. 3,878,201 (1975) as anti-malarial and anti-tubercular agents forwarm-blooded animals.

EXAMPLE 1 Preparation of1,5-bis(α,α,α-Trifluoro-p-tolyl)-1,4-pentadien-3-one(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl) hydrazone. ##STR2##

To a mixture of 2.1 g of5,5-dimethyl-1,4,5,6-tetrahydropyridinium-2-ylhydrazine hydroiodide and3.2 g of 1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadien-3-one in 6 ml ofabsolute ethanol was added one drop of 47% hydriodic acid. The mixturewas heated at reflux for 2 to 3 hours and then cooled in ice. The yellowhydroiodide salt which precipitated was collected by filtration andwashed with ethanol.

The hydroiodide salt was neutralized by stirring with 15 ml of ethylacetate and 15 ml of saturated sodium carbonate solution. The ethylacetate mixture was separated from the aqueous phase, dried overmagnesium sulfate, and concentrated to give a red oil. The oil was mixedwith a little ether, and the mixture refrigerated. The resulting solidswere collected and washed with ether and amounted to 1.2 g, meltingpoint 163.5°-164.5° C.

Analysis calculated for C₂₅ H₂₄ F₆ N₄ : C, 60.72; H, 4.89; N, 11.33.Found: C, 60.54; H, 4.73; N, 10.43.

The product exists in different crystalline forms, and whenrecrystallized from isopropyl alcohol, has a melting point of 189°-191°C.

EXAMPLE 2 Preparation of1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-Pentadien-3-one(1,4,5,6-tetrahydro-2-pyrimidinyl)hydrazone ##STR3##

27.7 Grams (0.075 mol) of the dienone and 18.0 grams (0.075 mol) of thehydrazine were reacted together in refluxing isopropanol for 3 to 4hours. The isopropanol was stripped away leaving a pale yellow solidwhich was washed thoroughly with ether. The yellow solid was stirredwith 200 ml of ether and 50 ml of saturated sodium carbonate. After 15minutes, the ether layer was dried and concentrated leaving a brightyellow solid weighing 25.0 grams (72% theory). A small sample wasrecrystallized from φCH₃ /hexane giving a bright yellow solid withmelting point 196°-197° C.

Analyses calculated for N₄ F₆ C₂₃ H₂₀ : C, 59.24; H, 4.29; N, 12.02.Found: C, 58.55; H, 4.53; N, 12.00.

EXAMPLE 3

The insecticidal activity of the compounds of the invention are furtherdemonstrated by the following tests, wherein pentadienone hydrazones areevaluated as stomach poisons against test insect species at rates offrom 500 to 10,000 ppm. Insect species utilized in these evaluationsare: American cockroaches [Periplaneta americana (Linnaeus)] and Germancockroaches [Blattella germanica (Linnaeus)]. Test formulations andevaluation procedures are as follows:

A. 100 Milligrams of 100% pure compound were placed in 20 g of creamypeanut butter and thoroughly mixed. This is equivalent to aconcentration of approximately 0.5% or 5000 ppm.

B. 5.0 Grams of peanut butter served as the control. Approximately 5.0 gof bait were placed in a 3 cm×1 cm high plastic cup. The plastic cup ofbait and a water wick were placed in a cage 8 inches in diameter and 2.5inches high. The bottom of the cage was an 8-inch diameter plate ofglass resting on a 1/2-inch rim which extended inward from the stainlesssteel side. Twenty (20) adult male German cockroaches or 12 nymphs ofAmerican cockroaches were placed in each cage. The cage was covered witha 16-mesh copper wire screen lid. The cages were held at approximately27° C.

The results are in the following table:

                                      TABLE I                                     __________________________________________________________________________                                           Percent Mortality                                                             German  American                                                              Cockroaches                                                                           Cockroaches                                                           Days    Days                                                          Concentration                                                                         Post-treatment                                                                        Post-treatment                 Compound                       in ppm  7   14  7   14                         __________________________________________________________________________     ##STR4##                      5000    100 100 17* 92                         Check (Control)                --      0    0  8    8                         __________________________________________________________________________     *Several affected.                                                       

EXAMPLE 4 Red Imported Fire Ants [Solenopsis invicta (Buren)]

Red imported fire ants [Solenopsis invicta (Buren)] obtainedout-of-doors under natural conditions were used in the imported fire antscreen. Approximately 0.5 cu. ft. of an active ant mound was placed in aplastic tub (13"×13"×8") and aged in the laboratory for 3 days beforeuse. The top 3 inches on the inside of the tub were dusted with talc toprevent the ants from escaping. Water was added to the mounds as neededboth before and after treatment to help keep them from becoming too dry.The compounds were dispersed in soybean oil starting at a lowconcentration of approximately 0.05%. The concentration was increased atvarious increments to approximately 1.0%. Low concentrations were usedfirst to determine if the compound was palatable to the ants.Approximately 7.5 g of soybean oil containing the toxicant were pouredover a small wad of absorbent cotton in a 3-oz. Dixie cup. The side ofthe Dixie cup was placed on top of the mound. Usually 3 tubs were usedper concentration. Mortality counts and/or ratings were made at 6 weeksafter treatment or longer if warranted. The temperature of the holdingrooms was approximately 26° C. with a relative humidity of approximately50%.

Data obtained are reported in the Table below.

                                      TABLE II                                    __________________________________________________________________________    Evaluation of Test Compound for the Control of the Imported Fire Ant          (Three Ant Colonies, Each Concentration)                                                                                    6-Week                                                                        Results                                                                       Number of                                                      Percent Bait   Colonies                        Structure                      Concentration                                                                         Acceptance                                                                           Alive or Dead                                                                          Remarks                __________________________________________________________________________     ##STR5##                       0.05   Fair to Excellent                                                                    All 3 dead                                                     1.0            Killed 1 of                                                                            Only majors                                                                   Alive in 2                                                                    Mounds at 3                                                                   weeks.                                                0.1     Attracted                                                                            Killed 3 to                                                                            1 Killed and                                                  the Ants                                                                             at 7 weeks                                                                             5 sick mounds                                                                 at 3                   __________________________________________________________________________                                                           weeks              

EXAMPLE 5 German Cockroach Bait Toxicant Test--[Blatella Germanica(Linnaeus)]

Test Procedure

Tests were conducted in cages 20.32 cm in diameter and 6.35 cm inheight. The circular side was made of stainless steel which supported apiece of glass 20.32 cm in diameter for the bottom. The cages werecapped with 16-mesh copper wire screen lids. One hundred, 25. and 6.25mg of technical compound were added to five grams of creamy peanutbutter in a plastic cup (inside dimensions of 8 mm high and 30 mm indiameter) to yield final concentrations of 2.0, 0.5, and 0.125%,respectively. The mixtures were each stirred for two minutes. One cup oftreated bait plus one cup of untreated lab chow (five grams) to serve asa choice of food, a 100 ml water wick, and 20 adult, male Germancockroaches were placed in each cage. The cages were held atapproximately 27° C. and 35% R. H. for mortality counts. Data obtainedare reported in the table below.

                                      TABLE III                                   __________________________________________________________________________    EVALUATION OF PENTADIENONE HYDRAZONES AS INSECTICIDES                         PERCENT MORTALITY                                                                                            German Cockroaches                                                            11-Day Mortality                               Structure                      2.0%                                                                             0.5%                                                                              0.125%                                  __________________________________________________________________________     ##STR6##                      100                                                                              100 100                                      ##STR7##                      100                                                                              100 100                                     __________________________________________________________________________

EXAMPLE 6 Imported Fire Ant Bait Toxicant Tests (Solenopsis invictaBuren)

Test Procedure

Tests were conducted in 30 ml disposable plastic medicine cups (40 mm IDat the top, tapering to 32 mm ID at the bottom, 38 mm high). A hole (6mm diam.) was drilled through the bottom of each cup and a layer ofplaster of Paris and builders' cement (9:1 ratio) was poured over thebottom. The plastic mixture covers the hole and acts as a wick to drawup water when the cup is placed on a saturated 1/4" foam pad. The cupswere placed in a tray and covered by another tray inverted to preventrapid evaporation of water from the foam pad. Moisture is necessary tokeep the humidity in the the cups high and thereby prevent dessiccationof the ants. The cement is added to make a hard mixture through whichthe ants cannot tunnel and escape.

Twenty worker ants from field-collected colonies were placed in eachtest chamber about 24 hours preceding start of the test. Thispretreatment holding period allows time for recovery of the ants fromhandling and for orientation to the containers.

Candidate chemicals were dissolved directly in the food material; e.g.,soybean oil. The toxic solution was offered to the ants on cotton swabssaturated with the material and placed in the test chamber in small vialcaps. Preliminary tests were conducted at concentrations of 1.0, 0.1,and 0.01 percent.

The ants were allowed to feed as desired on the toxic bait for 24 hours.After this exposure period, the toxicant was removed from the chamberand the ants remained without food for an additional 24 hours. At theend of this time new vial caps containing cotton swabs saturated withsoybean oil were placed in the chamber and left for the remainder of thetest period. Knockdown and mortality counts were made at intervals of 1,2, 3, 6, 8, 10 and 14 days following initial exposure. Each testconsisted of 3 replications. Room temperature was maintained at 75±2 F.Data are reported in the table below.

                                      TABLE IV                                    __________________________________________________________________________    EVALUATION OF PENTADIENONE HYDRAZONES AS INSECTICIDES                         PERCENT MORTALITY                                                                                            Red Imported Fire Ant                                                         14-Day Mortality                               Structure                      1.0% 0.1%                                      __________________________________________________________________________     ##STR8##                       69  100                                        ##STR9##                      100   95                                       __________________________________________________________________________

EXAMPLE 7

The insecticidal activity of the compounds of this invention isdemonstrated by the following tests, wherein pentadienone hydrazones areevaluated against test insect species at rates of from 10 to 1000 ppm.Test formulations and procedures used for evaluation are as follows:

Test Formulations.

A. 100 Milligrams of the test material is weighed, placed in a funnelover a 113 g narrow-mouth bottle, and rinsed into the bottle with a 35ml scoop of acetone, followed by a scoop of water and another scoop ofacetone to yield 1000 ppm in 65% acetone. If the material is notsoluble, it is broken up with a glass rod and used as a suspension.

B. This stock solution ("A") is used to make 300 ppm solutions orsuspensions by pipetting 30 ml of "A" into a bottle containing 70 ml of50% acetone to yield 300 ppm. Further dilutions in 50% acetone are madeas required.

C. Tests requiring 10 ppm acetone solutions: 1 ml of "A" is pipettedinto 99 ml of acetone to yield 10 ppm. Additional dilutions are madeusing 50% acetone as required.

Initial Tests Tobacco Budworm--[Heliothis virescens (Fabricus)].

A cotton plant with two true leaves expanded is dipped for 3 secondswith agitation in 300 ppm solution. A 1.27 cm to 1.91 cm square ofcheesecloth with about 50 to 100 budworm eggs 0-24 hours old is alsodipped in the test solution and placed on a leaf of the cotton plant,all being placed in the hood to dry. The leaf with the treated budwormeggs is removed from the plant and placed in a 226 g Dixie cup with awet 5 cm piece of dental wick and covered with a lid. The other leaf isplaced in a similar cup with a wick and a piece of cheesecloth infestedwith 50-100 newly hatched larvae is added before covering the cup with alid. After 3 days at 80° F., 50% r.h., observations of egg hatch aremade, as well as kill of newly hatched larvae, any inhibition offeeding, or interference of any sort with normal development.

Secondary Tests Tobacco Budworm--[ Heliothis virenscens(Fabricus)]--Third Instar

Three cotton plants with just expanded cotyledons are dipped in 1000 ppmsolution and placed in the hood to dry. When dry, each cotyledon is cutin half, and 10 are each placed in a 28 g plastic medicine cupcontaining a 1.25 cm dental wick saturated with water and onethird-instar budworm larva is added. The cup is capped and held for 3days at 80° F., 50% r.h., after which mortality counts are made.Compounds killing more than 75% of the larvae are further tested.

Cabbage Looper--[Trichoplusia ni (Hubner)]--Third Instar

A true leaf of a cotton plan is dipped into the test solution, agitatedfor 3 seconds, and removed to dry in an exhaust hood. When dry, the leafis placed in a 9.0 cm petri dish with moist filter paper on the bottom.Ten third instar larvae are added and the lid placed on the dish.Mortality counts are made after 3 days at 80° F. and 50±10% r.h.Compounds killing more than 75% of the loopers are further tested.

Southern Armyworm--Spodoptera eridania (Cramer)

Sieva lima bean plants pruned back to two expanded 3 to 4 inches primaryleaves are dipped 3 seconds with agitation in the treatment solutionsand then set in a hood to dry. After the leaves are dry they areexcised, and each excised leaf is placed in a 4-inch petri dishcontaining a piece of moist filter paper and ten third-instar Southernarmyworm larvae approximately 3/8 of an inch long. The petri dishes arecovered and placed in a holding room for 2 days at a temperature of 80°F. and 50% relative humidity. Mortality counts are made after 2 days.

Seven days after the plants are treated, leaves are again excised andthe test procedure repeated. Mortality of armyworms occurring in thistest demonstrates the residual activity of the compounds on the treatedleaves.

Data obtained are reported in the Table below.

                                      TABLE V                                     __________________________________________________________________________    Evaluation of Test Compound for Controlling Insects on Cotton Plants                                          Third                                                                         Instar                                                      Budworm           Tobacco                                                                             Cabbage                                                                             Southern                                        Eggs     Larvae   Budworm                                                                             Looper                                                                              Armyworm                                        300                                                                              100                                                                              10 300                                                                              100                                                                              10 1000                                                                             100                                                                              1000                                                                             100                                                                              1000                                                                             100                                                                              10 7                        Compound      ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              ppm                                                                              Days                     __________________________________________________________________________    1,5-bis(α,α,α-Trifluoro-                                                  0  -- -- 100                                                                              100                                                                              0  100                                                                               90                                                                              100                                                                              100                                                                              100                                                                              100                                                                              40 100                      p-tolyl)-1,4-pentadien-            100                                        3-one (1,4,5,6-tetrahydro-                                                    5,5-dimethyl-2-pyrimidinyl)-                                                  hydrazone                                                                     1,5-bis(α,α,α-Trifluoro-                                                  0  -- -- 100                                                                              100                                                                              0  100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              70 100                      p-tolyl)-1,4-pentadien-                                                       3-one (1,4,5,6-tetrahydro-                                                    2-pyrimidinyl)hydrazone                                                       __________________________________________________________________________

I claim:
 1. A method for controlling fire ants and cockroachescomprising contacting the insects, their habitat, breeding grounds orfeed with an insecticidally effective amount of a compound of theformula: ##STR10## wherein X is hydrogen or methyl.
 2. A methodaccording to claim 1 wherein the compound is1,5-bis(α,α,α-trifluoro-p-tolyl)-1,4-pentadien-3-one(1,4,5,6-tetrahydro-5,5-dimethyl-2-pyrimidinyl)hydrazone.
 3. A methodaccording to claim 1 wherein the compound is1,5-bis(α,α,α-trifluoro-p-tolyl)1,4,-pentadien-3-one(1,4,5,6-tetrahydro-2-pyrimidinyl)hydrazone.
 4. A method according toclaim 1 wherein the insects are fire ants.
 5. A method according toclaim 1 wherein the insects are cockroaches.